Azo dye



Patented June 16, 1942 AZO DYE Chiles E. Sparks, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Original application June 25, 194-0,

Divided and this application November 14, 1940, Serial No. 365,610

(or. 260l54) Serial No. 342,289.

12 Claims.

This invention relates to new tetrakisazo compounds, to dyeings on cellulosic fibers, such as cotton and regenerated cellulose which are produced with such compounds by dyeing the fibers cyclo-alkane series having 4 to 6 carbons in the ring and ring substituted straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and is present once to two less than the number of carbons in the ring, and a radical of the diazacycloalkane series having 3 to 6 carbons in the ring and the straight and with a type of di(amino-phenoxy-alkyl-acyl- 5 branched chain alkyl derivatives thereof in which amino)a1kanes, diazotizing and developing in the alkyl has 1 to 6 carbons and is substituted in the fiber with suitable coupling components, and to ring carbons once to twice the number of carbons processes of making such compounds and dyein the ring; [C(R)2l represents the group coningssisting of straight and branched chain aliphatic Various disazo compounds having substantivity 10 radicals wherein R occurs twice as indicated and for cotton and regenerated cellulose and which the symbol R, represents like and unlike memcan be tetrazotized on the fiberand coupled with bers of the group consisting of hydrogen and alkyl coupling components to form dyeings of excellent radicals containing 1 to 6 carbon atoms. Of these fastness and good insolubility are known; but in aliphatic radicals, there may be 1 to 10 as repremany cases the dyeings developed from such subsented by the subscript n, for example stantive tetrazotizable compounds do not have as [C(R) good brightness as is desired. 2

It is among the objects of this invention to includes such radicals as provide new tetrakisazo compounds. Another H H H H object of the invention is to provide developed I I I dyeings of improved brightness, washing fastness, CHT" discharge properties and other properties desired alkyl H a y a y in developed dyeings. Other objects of the inand vention will be apparent from the following de- H H scription. The objects of the invention are attained in I 1 general by providing a compound which may be H alkyl made by tetrazotizing one of a class of di-amino- Where alkyl may be any saturated aliphatic phenoxy-alkyl-acylamino) alkanes and coupling hydrocarbon radical containin 1 0 6 CaYbOII with a class of suitable arylamines. This tetraatoms; R. is from the group consisting of hyzotizable disazo compound is substantive to cotdrogen, alkyl with 1 to 6 carbon atoms, alkoxy ton and regenerated cellulose. It is dyed on the with l to 6 carbon atoms, halogen, CN, carboxy fiber, tetrazotized thereon and developed with a and sulfonic acid; m is 1 to 4; and YNH2 is suitable azo dye coupling component which is the radical of an amino-substituted coupling devoid of solubilizing groups to form the finished 5 component from the group consisting of certain dyeing. The substantive dyes are represented in arylamines of the benzene and naphthalene general by the formula phenyl-amino-naphthol sulfonic acids, amino- /1IN=N 0 o 1 N=NYNH: NH: 5 oo (Baird-1% H [C(R)2]-O l 5 wherein D represents a radical of the groups phnyl-aminomaphthfl Sulfonic acids, aminoconsisting of the polymethylene diamines having benzoyl-amino-naphthol sulfonic acids, amino- 2 to 10 methylene groups and straight and benzoyl-amino-benzoylamino-naphthol sulfonic branched chain alkyl derivatives thereof in which acids and amino-phenyl pyrazolones. alkyl has 1 to 6 carbons and is substituted in the The invention will be more fully set forth in methylene groups once to twice the number of the following more detailed description which inmethylene groups, a radical of the diaminoeludes examples that are given as illustrative embodiments of the invention and not as limitations thereof. Parts are expressed in parts by weight unless otherwise noted.

Example I A slurry was made consisting of 143 parts of l,2-di(4 amino phenoxy acetylamino) ethane and 2000 parts of water. It was acidified by adding '73 parts of 100% hydrochloric acid as a 30% solution. The mixture was cooled by adding ice to C. and 55 parts of 100% sodium nitrite were then added. Tetrazotization was continued at 0-5 G. for hour whilst maintaining a slight excess nitrite.

A slurry containing 295 parts of 2(3'-aminobenzoylarnino)-5-naphthol-7-sulfonic acid and 2000 parts of water was made. An aqueous solution of ammonia in suificient quantity for complete solution and a slightly alkaline reaction to Brilliant Yellow paper was added and then '7 parts of sodium-bicarbonate were added. The

Five parts of cotton piece goods were dyed from a water solution of the compound in the usual manner known to those skilled in the art, using two-tenths parts of the dye. The dyed fabric was rinsed in cold water and then put into 2000 parts of water at C. The compound was tetrazotized on the fiber by adding three parts of sodium nitrite and four parts of sulfuric acid to the water and stirring for 15 minutes. The piece was rinsed with cold water and then put into a solution which was made by dissolving one part of beta-naphthol in 2000 parts of water and one-half part of caustic soda. The solution was stirred rapidly while adding the rinsed piece goods and stirring was continued for 15 minutes. The fabric was then rinsed in cold water and dried. The dyeing was a scarlet shade. The dye on the fiber is represented by the formula Example II A dye represented by the formula 1,2-di-(4'- amino-phenoxy-acetylamino) -ethane 3 (1-(3'- aminophenyl) 5 pyrazolone-3-carboxylic acid) 2 was prepared by a procedure similar to Example I except that 180 parts of 1-(3-amino-phenyl)- 5-pyrazolone-3-carboxylic-acid were used instead of 295 parts of 2-(3'-amino-benzoyl-amino) -5- naphthol-7-sulfonic acid. The resulting dye was an orange powder, and had properties similar to the substantive compound of Example I. It is at -85 C. in an oven. The dry product had 5 represented by the formula ton and similar fibers. The product is represented by the formula OGHzCNHOHzCH2-NH When dyed and developed on the fiber with beta naphth'ol in a manner similar to that described in Example I the dyeing was an orange OH I I SOaNa shade. The structure of the dye on the fiber is represented by the formula Example I When dyed on cotton fiber and developed with A dye represented by the formula beta naphthol in a manner similar to that deammo'phenoxy'acetyl) 'plperazme 3 [2(4 20 scribed in Example I the dyeing was a red shade.

no-benzoylamino) 5 -naphthol 'Y-sulfonic acid]z was made by following the procedure of Example The dye on the fiber 1s represented by the I except that 153.5 parts of 1,4-di(4-aminomula CHaG Ha 1 1 OOCHa(|%-N N- Jc11z-0- -N N o OHzOHz (L 1 1 NaOaS- -NHC=0 O=(|JHN soaNa OH- Q 011 N N ll II phenoxy-acety1 -p iperazin e was used instead of The following products were prepared by meth- 122 of $1232 "s' g i ie f' g i' ods similar to those of the foregoing examples. no 6 ane an par s O enzoy The .properties of these products were in general amino) -5-naphthol-7-sulfonic acid was used instead of 295 parts of 2-(3-amino-benzoy1amino) 45 slmllar to the Products of the foregomg examples 5-naphtho1-7-sulfonic acid. The product in the except for variations in shade. The shades listed 'IltO 1 i y p w i an ol l p t g i opposite each product are the shades of the dyean 1 s 0 er proper ms were s1m1 ar 0 ose o in s on Cotton when dev 10 h h r the product of Example I. The product is repg e ped Wlt .t e couplmg resented by the formula 50 component mdlcated- CHgGHa N-OO-(LHr-(P-N NO-CH:O N [I II ll ta-2i new [I N O CHzCHz 0 N NaOgS -NH-(|7=O O=?HN SOaNa OH Q OH NH: NH:

. Developed Example Oombmatlcn with Shade IV 1,2-di(4-aminophenoxy-acetylamino)-ethane 3 (2-amino-5- Beta naphtho1 Bordeaux.

naphthol-7-sulfonic acid. V 1, 2-di(4-aminophenoxy-acetylamlno)-ethane [2(4-amino-3- do Maroon.

sulfo phenylamino)-5-naphtho1-7-Sulfonic acidh. VI 1,2-di(4-amino-2-su1fo-phenoxy-acetylamino)ethane :3 (2- do Red.

amino-5-naphthol-7-sulfonic acidh. VII 1, 2-di(4-amino-2-sulfo-phenoxy-acetylamino)-ethane 3 [2(3- do Orange.

amino-benzoylamino)-5-naphthol-7-sulfonic acidh. VIII 1, 2-di(4-amino-2-sulfo-phenoxy-acety1amino)-ethane 3 [2(4- ,d0 Do.

amino-benzoylamino)-5-naphtho1-7-su1fonic acidlz.

1,3-di [a1pha(3'-amino phenoxy heptanoylami+ no) l-propane,

1,3 di[beta(3'-amino-phenoxy-butyrylamino) heptane,

1,2-di(4- amino-2'-sulfo-phenoxy-acetylamino) ethane,

1,2-di(4-amino phenoxy acetylamino) -1,2-dimethyl-ethane,

1,2-di[beta-(4- amino phenoxy propionylamino) -ethane,

1,2-di(2'- methyl -5'- a-mino-phenoxy-acetylamino) -ethane,

1,4-di[a1pha-ethyl-beta( 3 -amino-.phenoxy) -propionylaminol -4-methyl-3-ethyl-pentane,

1, 4-di(4'-v amino phenoxy acety1amino)-cyc1obutane,

1,4-di(4'-amino phenoxy acetylamino) -2,5-dimethyl-cyclohexane,

1,4-di(4-amino phenoxy acetyl) -2-methyl-piperazine and 1,4-di(4'-amino-phenoxy-acetyl) 2,5 dimethylpiperazine As the Y-NH2 or coupling components indicated in the general formula the following are the classes:

(1) Arylamines of the benzene and naphthalene series represented by the formulae in which one R' is hydrogen and the other is hydroxy and the M which is meta to hydroxy is SO3H and the other is hydrogen.

acids and amino-benzoylamino-benzoylaminonaphthol sulfonic acids represented by the formulae (5) Amino phenyl pyrazolones represented by the formula in which R" is one of a group consisting of alkyl and carboxyl.

As illustrative of the many second components which can be used to produce the dyes having the characteristic structure and properties of those specifically described, the following are mentioned: 3-amino-anisole, l-naphthylaminefi-sulfonic acid, 2-amino-5-naphtho1-7-sulfonic acid, 2- (4'-amino-3-sulfo-phenylamino) -5- naphthol-'l-sulfonic acid, 2-(4'-amino-benzoylamino) -5-naphthol-'7-su1fonic acid, 1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid, aniline, S-amino-toluene, 2,5-diniethoxy-aniline, Z-methoxy-aniline, 2-meth0Xy-5-methylaniline, l-amino-naphthalene, 1-amino-2-methoxy-naphthalene-fi-sulfonic acid, l-amino-naphthalene-G- carboxylic acid, 1,8-amino-naphthol-3,6-disulfonic acid, 2-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-3,5-disulfonic acid, 1- amino-8-naphthol-4-sulfonic acid, 1-amino-5- naphthol-7-sulfonic acid, 2-amino-8-naphtho1- fi-sulfonic acid, 1-amino-5-naphthol, 2(3'-aminobenzoylamino) -5-naphthol-7-sulfonic acid, 1-(4- aminobenzoy1amino)- 5 naphthol 7 sulfonic acid, 2 [4- (4 '-amino-benzoylamino) -benzoylamino]-5-naphthol-7-sulfonic acid, 1- (4'-aminobenzoylamino) -8naphthol-4-sulfonic acid, 1- (4'-amino-phenyl) -5 pyrazolone 3 carboxylic acid, 1-(3-aminopheny1) -3-methyl-5-pyrazolone, 1- (4'amino-phenyl) -3-methyl-5-pyrazolone, 1- (2'methoXy-5'-amino-phenyl) 3-methyl- 5 -pyrazolone, 1 -(4'- amino 3'- carboxy phenyl) -3- methy1-5-pyrazolone, 1-(4'amino-3-su1fo-phenyl)-5-pyrazolone-3-carboxylic acid, l-(2'-methyl-5-aminophenyl) -3-methyl-5-pyrazolone, 1- (2'-methyl- 5'-amino-phenyl) 5 -pyrazolone- 3 carboxylic acid and 1-(2'-chloro-5-amino-phenyl) -5-pyrazolone-3-carboXy1ic acid.

The substantive dyes contain at least two solubilizing groups such as carboxyl and sulfonic acid but more can be present.

As developing components 1-phenyl-3-methyl- S-pyrazolone, metal-toluylene diamine or acetoacet anilide can be used as well as beta naphthol. These coupling components produce developed dyeings having similar superior fastness, discharge and brightness properties as those produced by developing with the beta naphthol and variations in shade can be attained by selection of the coupling component.

The first components of the azo compounds can be made by condensing a diamino alkane, a diamino-cyclo-alkane or a diaza-cyclo-alkane of the kinds described, such as a compound represented generally by the formula NH2-DNH2 with a nitro acyl halide of the type and then reducing the nitro groups of the di- (nitro phenoxy acylamino) alkane, -cyclo-alkane or -diaza-cyc1o-alkane to amino. In general the condensation can be carried out readily at about to 20 C. in the presence of a basic EN=N=NYN condensing agent such as an alkali-metal hydroxide and in a medium comprising a non-reactive organic solvent, such as ethylene dichloride. ducticn of the nitro groups can then be separated and the products can be tetrazotized by methods which are in general well known in the art.

The tetrazotizable products are substantive to cotton, regenerated cellulose, various vegetable fibers and similar dyeable substances. When they are tetrazotized and developed on the fiber with the described azo dye coupling components they have excellent fastness to washing, they do not appreciably stain associated undyed fibers during washing'and they have goodgeneral properties which are desirable in dyed fibers. When developed on the fibers the brightness of the dyeing is superior as compared with dyeings of like shade which are made with quite similar dyes which do not contain the phenoxy group. For example a dyeing on cotton made with 1,2-di(4- amino-phenoxyacetylamine) ethane and developed with beta naphthol is brighter than one made on cotton with 1-,2-di ('4-aminobenzoylamino)-'ethane and developed With beta naphthol.

This is a division of my application Serial No. 342,289.

From the foregoing disclosure it will be recognized that the invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

I claim:

1. An azo compound represented by the formula to 10 methylene groups and the straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and in which the methylene groups are substituted once to twice the number of methylene groups, a radical of the diamino-cyclo-alkane series having 4 to 6 carbons in the ring and the monoand dimethyl derivatives thereof, and a radical of the diaza-cyolo-alkane series having 3 to 6 carbons in the ring and the mono-di-methyl derivatives thereof; 11. is 1 to 6; each R is from the group consisting of hydrogen, alkyl having 1 to 6 casbons, the corresponding alkoxy groups, halogen, CN, carboxy and sulfonic acid; m is 1 to 4; and each Y is the radical of a coupling component from the group consisting of arylamines of the benzene and naphthalene series, amino naphthol sulfonic acids, amino-phenyl-amino -naphthol sulfonio acids, amino-benzoylamino-naphthol sulfonic acids, amino-benzoylamino-benzoyl- The primary diamines formed after re- )m in which D represents a radical of the group consisting of the polymethylene diamines having 2 to 10 methylene groups and the straight and branched chain alkyl derivatives thereof in which alkyl has 1 to 6 carbons and in which the methylene groups are substituted once to twice the number of methylene groups, a radical of the diamino-cyclo-alkane series having 4 to 6 carbons in the ring and the monoand di-methyl derivatives thereof, and a radical of the diazacyclo-alkane series having 3 to 6 carbons in the ring and the monoand di-methyl derivatives thereof; n is 1 to 6; each R is from the group consisting of hydrogen, alkyl having 1 to '6 carbons, the corresponding alkoxy groups, halogen, CN, carboxy and sulfonic acid; m is 1 to 4; each Y is the radical of a coupling component of the benzene and naphthalene series from the group which is represented by the following formulae hydroxy; the M which is meta to 'hydroxy is NH CO ii i I Rom,

and

wherein R," is one or any combination of the 40 group consisting of hydrogen, alkyl having 1 to 6 carbons, and the corresponding alkoxy groups; 70 is 1 to 2; the symbol -H denotes the coupling position; one R is hydrogen and the other is SO3H and the other is hydrogen; and R" is one of a group consisting of alkyl having I to 6 carbons and carboxyl; and each E is the radical of one of a group consisting of 1-pheny1-3- methyI-B-pyrazolone, meta-toluylene diamine, acetoacet anilide and beta naphthol; said compound having at least two solubilizing groups.

3. An azo compound represented by the formula cyclo-alkane series having 3 to 6 carbons in the ring and the monoand di-methyl derivatives thereof; n is 1 to 6; each R is from the group consisting of hydrogen, alkyl having 1 to 6 carbons, the corresponding alkoxy groups, halogen, CN, carboxy and sulfonic acid; m is 1 to 4; and each Y is the radical of a coupling component of the benzene and naphthalene series from the group which is represented by the following formulae 1 nd wherein R" is one or any combination of the EEC u// group consisting of hydrogen, alkyl having 1 to 6 carbons, and the corresponding alkoxy groups; k is 1 to 2; the symbol H denotes the coupling N 5 position; one R is hydrogen and the other is hydroxy; the M which is meta to hydroxy is SO3H and the other is hydrogen; and R."" is one of a group consisting of alkyl having 1 to 6 carbons and carboxyl. 10 4. The compound represented by the formula 5. The compound represented by the formula 6. The compound represented by the formula CHzCHz 7. Fiber dyed with the dye of claim 1. 8. Fiber dyed with the dye of claim 2. 9. Fiber dyed with the dye of claim 3. 65 10. Fiber dyed with the dye of claim 4.

11. Fiber dyed with the dye of claim 5. 12. Fiber dyed with the dye of claim 6.

CHILES E. SPARKS.

Certificate of Correction Patent No. 2,286,392. June 16, 1942. CHILES E. SPARKS I It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correctlon as follows: Page 1, second column, line 37, for phenyl-amino-naphthol read series, amino-naphthol; page 6, second column,

line 10, for mono-di-methy read monoand di-methyl; same page, line 28, in the formula, for E-N=N=N-Y-N read EN=N-YN=N; page 7, first column, line 12, for that portion of the formula reading read CO-; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the ease in the Patent Office.

Signed and sealed this 4th day of August, A. D. 1942.

(SEAL) HENRY VAN ABSDALE,

Acting Commissioner of Patents. 

